Sulfur dye and process of making same.



- Breslau 1895, Vol. II, pp.

EDWARD s. QHAPIN, or NEW roan, N. Y.

SULFUR DYE Aim rnoonss or MAKING SAME.

Specification of Letters Patent.

Patented Jan. 12, 1909.

Application filed February 20, 1906., Serial No. 301,980. (Specimena) Toall whom it may concern:

Be it known that I, EDWARD S. CHAPIN, a citizen of the United States,residing in the borough of Brooklyn, city and State of New York, haveinvented a new and useful Improvement in of Makin the Same, is a specication.

My invention consists in heating a noncrystallizable polysaccharid withan aromatic chemical and sulfuring substances until a dyestufi isproduced.

I have discovered that by heating to a proper degree of temperature andfor a suflicient len th of time a non-crystallizable polysacchari(Tollens "Kohlenhyd1=ate, 197-276) With an aromatic chemical andsulfuring substances, a valuable dyestuif is produced, which will dyecotton directly in a salt bath with the assistance of sodium sulfid orsal soda.

1 may use an aromatic chemical which in itself is a color-former, andfind, in such a case, that the resulting substance and shade of whichthe following are different from those resulting from the.

sulfuring of the aromatic chemical alone, or of the non-crystallizablepolysaccharid alone, or of the mixture of the separately sulfuredsubstances. Here the non-crystallizable polysacch'arids may be said toplay the part of co-bases. I may also use an aromatic chemical which initself is not a color-former and when sulfured alone under similarcircumstances produces no coloring matter, and find in some such casesthat the resulting substance and shade are difierent from thoseresulting from the sulfuring of the non-crystallizable polysaccharidalone. This seems to indicate that color-forming properties have beenimpartcdto the-noncolor-forming aromatic chemical by the non--crystallizable polysaccharid. The influence of increments of'heatfurthermore in connection with many of these co-basis colors, forexample with the colors obtainable from wheat starch and metaphenylenediamin,'is characteristically novel. While with the coloring mattersproduced from the non-crystallizable polysaccharids alone the higherthe'temperature at which the standard cotton colors can be made theblacker "the result; and with the colors produced from aromatic basesalone the lowest temperatures possible for the sake of beauty of shade.

usually below 175-150 Q. are now sought Sulfur Colors and Process hourgradually to 300 C.

(see Bots, Textile Colorist 1904:, No. 307, p. 200); with many of theco-basis colors and in particular with the example cited, the higher thetemperature below 300 C. the brighter and the richer are the colors thatare thereby obtained.

The coloring matters obtained are characterized by their fastness: theyare fairly fast to light, but much faster to falling, alkalies andacids. When these coloring matters are after-treated with bichromate ofpotash, chromium fluorid, or blue stone, the shades are dulled, but-thefastness of the results is much increased. The same or even greaterfastness be secured by including in the original melts as an ingredientblue stone:- in this case the shades of the resultant coloring mattersare unaltered, and the direct dyeings possess all the very excellentfastness of after-treated dyeings. 1

The following examples ma serve 'to show the manner in which coloringmatters may be produced by sulfuring various noncrystallizablepolysaccharids in combination with various color-forming aromaticchemicals.

Ewample 1. Wheat starch and 'netaplwnlylem dz'amin.-Into a suitablecrucible weigh grams of sodium sulfid crystals, and 15 grams of sulfur.water and boil for five minutes. 10- grams a thin paste in 50 c. c. ofwater. Then add 6 grams of metaphenylene diamin. Boil slowly until thewater has evaporated. Then raise the temperature in one half an Continueheating at 300 C. for another half hour. Stir frequently in order tobring abont a COH1- plte reaction throughout the mass. In heating andstirring great care mustbe taken to prevent burning. In case the fulltinctorial power or the richest shade of the coloring matter has notbeen developed, heat another half hour at 300 C. The coloring matterthus formed is readily soluble in cold water, or in cold alcohol, to abright Then add brown solution; it is readily soluble in cold causticsoda or carbonate of solutions. it dyes cotton a fast cutch brown shadein, as salt bath withthe assistance of sodium sulfid or sal soda.

The colorin principle can be obtained in a purer an more concentra formby of the coloring matters may Add 200 .c. c. of

of wheat starch Worked up into precipitating with acids in thewell-known manner; the coloring matter thus obtained is insoluble inWater, or in cold'alcohol,

soluble in a bright cutch-brown shade, and'dyes cotton direct from asalt bath with the assistance of sal soda and sodium sulfid fast cutchbrown shades.

- If in the above formula the metaphenyl. ene diamin is increased to 12grams a much brighter brown will be produced while if the amount bedecreased to 3 grams a duller brown will be produced.

v The coloring matters obtained are of a and of an excellent relativedegree of fastness to fulling, alkalies and acids.

- coloring matters can be obtained by aftertreating with metallic salts,

as bichromate of potash, chromium fiuorid, or blue stone. The dyeingsafter-treated with bluestone are especially fast to light. 3 grams ofblue stone may be included in the original melt.

-'llhe shades of the Resulting coloring mat-' ters are uninfluenced bythe presence of the metallic component of the melt, and the fastnesstowards agents becomes generally.

a excellent.

' hwample ll. Cornstarch one diamin.F or wheat I substitute corn starch.oring matter is substantially identical with and metaphenylthat ofExample I.

Ewample Ill. Potato starch and metaphenylene' diamin-For Wheat starch inExample I substitute ,potatostarch. The 'I'GSUltlIl coloring matter issubstantially identica with that of Example I. I

Example "I V. Gum arabz'c and metaphem Zcne diamin.For wheat starch inExample' I substitute gum 'arabic and use more water at the start.The-resulting coloring matter is substantially identical with that .ofExample I. l

Ewample V. Wood sawdust and metaphonylene diamin.Into a suitablecrucible weigh out 60 grams of sodium sulfid crystals and 15 gramsiofsulfur. Boil up to dissolve the sulfur. Then add 10 grams of woodsawdust and 6 grams enev diamin. Boil one hour to impregnate the sawdustthoroughly with the sulfuring agents. Then raise the temperature slowlyto 320 C. covering the crucible,to prevent the burning of the contents.Heat at 320 C. for one hour or-until the full strength of the color hasbeen develo ed.

The coloring matter obtained'is readily soluble in cold water, coldalcohol, cold alkaline and cold sodium sulfid solutions-to a dull cutchbrown solution and dyes cotton direct in a salt. bath, fast, dull cutchbrown shadesywlth the assistance of sodium sulfid or sal soda.

The coloring principle can be obtained solution of sodium sulfid to agood relative degree of fastness to light,

Faster starch in Example The resulting col-,

of metaphenylconcentrated form by in a purer and more precipitating withacids in the Well-known manner: the-coloring matter obtained isinsoluble in water and alcohol, soluble in a solution of sodium sulfidto a dull cutch brown shade, and dyes cotton direct in a salt bath withthe assistance of alkali and sodium sulfidfast dull cutch brown shades.

Example VI. N onorystallizable polysaccharz'd andmetanitraniZin.-Substitute metanitranilin, gram for-gram, for metaphe-IV The resultant products will be similar in characteristics to thoseobtained by the use of metaphenylene diamin, though generally rather andshade.

Ewample VII; Nonorystallz'aable polysaccharids andmetadz'm'trobenzene.-Formetaphenylenediamin in Examples I, II, III- andIV substitute gram for gram, metadini- .nylene diamin in Examples I, II,III and poorer relatively,'in strength 'trobenzene. The resultingcoloring matters are similar in fastness and other'characteristics tothose obtained by the use of metaphenylene diamin, but the shades aredarker, "slightly so with thestarches, and decidedly so wlth woodsawdust.

. I have made many other experiments with mynew process. Thusfrom'binitro- 'chlorbenzol and cornstarch I have obtained illustrate themanner in which coloring matters may be produced from thenon-crystallizable polysaccharids in combination with non-color-formingaromatic chemicals.

Ewample VIII Wheat starch and sodium salt of sulfam'lic acid.Weigh intoa crucible 60 grams of sodium sulfid crystals and 15 grams of sulfur,and 10 grams of wheat starch. Melt and heat for 1 hour at 120C. Add 6grams of the sodium salt of sulfanilic acid. Heat at 120140 C. until thecolor forms; then raise. the temperature to 200 and heat for an hourmore.

The color formed is a medium, not dark,

reddish brown. It is soluble incold water and cold alcohol, in coldalkaline and cold sodium sulfid solutions to a medium brown solution,and dyes cotton dirwt from a salt" bath with the assistance of 'sal sodaor sodium sulfid fast 1 medium brown not dark shades.

\IVith corn or similar..

Example IX. Starch. and sulfam'lic potato starch the results are thesodium salt of sulfanilic acid, in Example VIII, similar results will beobtained.

Without the addition of the starch in the above examples, no dyestufi'swould be produced by the process given,while with the starch alone adark brown would be obtained. i

I claim: v1. The process for the roduction of sulfur dyes which consists1n heating a noncrystallizable polysaccharid with an aromatic-chemicaland sulfurin substances.

2. The process for the pro uction of sulfur dyes which consists inheating a noncrystallizable polysaccharid with a colorforming aromaticchemicaland sulfuring substances. I

3. The process for the production of sulfur dyes which consists inheating a noncrystallizable. polysaccharid with' a color-- formingaromatic chemical, sulfur and sodium sul d, substantially as described.

4. The process for the production of sulfur dyes which consists inheating a starch with an aromatic chemical, and sulfuring substances.

5. The process for the production of sul fur substances which consistsin heating a starch with a color-forming aromatic chemical and sulfuringsubstances.

6. The process for the production of sulfur dyes which consists 1nheating wheat starch with an aromatic chemical and-sulfuring substances.

7. The process for the production of sul- "acz'dr-By substitutingsulianilic acid for fur dyes which consists in heating wheat starch witha color-forming aromatic chemical and sulfuring substances.

8. The process for the production of sulfur dyes which consists inheating wheat starch and metaphenyle'ne diamin with sulfuringsubstances.

9. The process for the production of sulfur dyes which consists inheating wheat starch, metaphenyle'ne diamin, sulfur and sodium sulfid,substantially as described.

10. As a new articleof manufacture, the brownv coloring matter which canbe made from wheat starch, and metaphenylene diamin, substantially asdescribed, which is soluble in cold water, or in cold alcohol, to abright brown solution, is readily soluble in cold caustic soda orcarbonate of soda solutions, and which dyes cotton a fast cutch brownshade in a salt bath with the assistance of sodium sulfid or sal soda,and which, when precipitated by an acid forms a brown cbloring-matterwhich is insoluble in water, or in cold alcohol, soluble in a solutionof sodium sulfid to a bright cutch brown shade, and dyes cotton directlyfrom a salt bath with-the assistance of sal soda. and sodium sulfid fastcutch brown shades.

In testimony whereof, I have hereunto signed my name in the presence oftwo subscribing witnesses'.

EDWD scnar'ru.

JOHN A.

